ABSTRACT
The interface-solute interactions, including solute location, surfactant charge, and geometry of solute interactions were studied in CTAB micelles and reverse micelles and were found to be similar as measured using (1)H NMR spectroscopy and a pH-sensitive probe. (1)H NMR spectra were recorded in the presence and absence of 2,6-pyridinedicarboxylate probe at CTAB concentrations above and below the critical micelle concentration showing interaction between dipic-probe and the micellar self-assembled structure. Downfield chemical shifts are observed for the CTAB surfactant signals upon aggregation and micelle formation. The effect of micelle formation on CTAB chemical shifts was quantitated, and simple ion pairing was ruled out. No significant change in CTAB surfactant signals are observed in the presence of monoanionic probe, whereas significant shifts are observed in the presence of the dianionic probe. The (1)H NMR spectra of the dipic-probe are diagnostic of the protonation state and isomeric form of the dipic-probe. The (1)H NMR chemical shifts in micelles are sensitive to the location of the dipic-probe, and the downfield chemical shift suggests location of part of the molecule in the Stern layer near the charged interface. Other parts of the probe show an upfield chemical shifts consistent with a deeper penetration of the dipic-probe into the surfactant layer. Probe location was confirmed using the 2D ROESY. Spectra recorded of the dipic-probe at various pH values demonstrate that both CTAB micellar and CTAB/pentanol/cyclohexane reverse micellar interfaces are different than those reported in aqueous solution and in AOT/isooctane reverse micelles (Crans et al. J. Org. Chem. 2008, 73, 9633-9640) and suggest interface penetration by dipic(2-). Together these observations and comparisons provide guidelines for future interpretation of chemical shift changes in both micelles and reverse micelles and point to headgroup charge as being a key factor determining the direction of chemical shift change and the depth of solute penetration.
